Segmented copolyester adhesive and coating compositions

ABSTRACT

THERMOPLASTIC ADHESIVE AND COATING COMPOSITIONS WHICH COMPRISE (A) ABOUT 1 TO 99 PERCENT BY WEIGHT OF THERMOPLASTIC SEGMENTED COPOLYESTER ELASTOMER CONSISTING ESSENTIALLY OF A MULTIPLICITY OF REDUCING SHORT CHAIN ESTER UNITS ANDLONG CHAIN ESTER UNITS JOINED THROUGH ESTR LINKAGES, SAID SHORT CHAIN ESTER UNITS AMOUNTING TO ABOUT 15 TO 75 PERCENT BY WEIGHT OF SAID POLYESTER AND BEING DERIVATED FROM AROMATIC DICARBOXYLIC ACID SUCH AS TEREPTHALIC ACID, OR A MIXTURE OF TEREPHTHALIC AND ISOPHTHALIC ACIDS, AND AN ORGANIC DIOL SUCH AS BUTANEDIOL AND SAID LONG CHAIN ESTER UNITS AMOUNTING TO ABOUT 25 TO 85 PERCENT BY WEIGHT OF SAID COPPOLYESTER AND BEING DERIVED FROM AROMATIC DICARBOXYLIC ACID SUCH AS TEREPHTHALIC ACID, OR AMIXTURE OF TEREPHTHALIC AND ISOPHTHALIC ACIDS, AND   A LONG CHAIN GLYCOL SUCH AS POLYTETRAMETHYLENE ETHER GLYCOL, SAID COPOLYESTER HAVING A MELT INDEX OF LESS THAN ABOUT 150 AND A MELTING POINT OF AT LEAST ABOUT 125* C., AND (B) ABOUT 1 TO 99 PERCENT BY WEIGHT OF ONE OR MORE LOW MOLECULAR WEIGHT THERMOPLASTIC RESINS INCLUDING HYDROCARBON RESINS SUCH AS COUMARONE-INDENE RESINS, PETROLEUM RESINS, STYRENE POLYMERS, CYCLOPENTADIENE RESINS AND TERPENE RESINS, BITUMINOUS ASPHALTS, COAL TAR PITCHES ROSINS, PHEOLIC RESINS, CHLORINATED ALIPHATIC HYDROCARBON WAXES, AND CHLORINATED POLYNUCLEARAROMATIC HYDROCARBONS.

United States Patent 9,800 Int. Cl. C08g 11/16, 39/00 US. Cl. 260-26 30Claims ABSTRACT OF THE DISCLOSURE Thermoplastic adhesive and coatingcompositions which comprise (A) about 1 to 99 percent by weight ofthermoplastic segmented copolyester elastomer consisting essentially ofa multiplicity of recurring short chain ester units and long chain esterunits joined through ester linkages, said short chain ester unitsamounting to about 15 to 75 percent by weight of said copolyester andbeing derived from aromatic dicarboxylic acid such as terephthalic acid,or a mixture of terephthalic and isophthalic acids, and an organic diolsuch as butanediol and said long chain ester units amounting to about 25to 85 percent by weight of said copolyester and being derived fromaromatic dicarboxylic acid such as terephthalic acid, or a mixture ofterephthalic and isophthalic acids, and a long chain glycol such aspolytetramethylene ether glycol, said copolyester having a melt index ofless than about 150 and a melting point of at least about 125 C., and(B) about 1 to 99 percent by weight of one or more low molecular weightthermoplastic resins including hydrocarbon resins such ascoumarone-indene resins, petroleum resins, styrene polymers,cyclopentadiene resins and terpene resins, bituminous asphalts, coal tarpitches, rosins, phenolic resins, chlorinated aliphatic hydrocarbonwaxes, and chlorinated polynuclear aromatic hydrocarbons.

CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part ofapplication Ser. No. 151,477, filed June 9, 1971, now abandoned, whichin turn is a continuation-in-part of application Ser. No. 100,291, filedDec. 21, 1970, now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the Invention This inventionrelates to compositions containing a thermoplastic, segmentedcopolyester elastomer and one or more compatible low molecular weightthermoplastic resins. These compositions are useful in a wide variety ofapplications including uses as hot melt adhesive compositions andcoating compositions.

(2) Description of the Prior Art Hot melt adhesive compositionscontaining low molecular weight thermoplastic resins are not new. Inrecent years hot melt compositions, such as those containing ethylene/vinyl acetate copolymers, have found broad uses in applications such asadhesives for edge banding in furniture manufacture, surface laminating,shoe assembly, pressure sensitive adhesives, and paper coatings forpackaging. However, the use of these hot melt compositions is limited toa narrow temperature range. For example, most ethylene/vinyl acetatecopolymer-based hot melt compositions lose their strength attemperatures as low as about 80 C.

Much research has been carried out in recent years to provide hot meltcompositions having improved high temperature performance. New hightemperature resistant hot melt adhesives are now being introduced to themarket, but these compositions either do not have the superior adhesivestrength of typical ethylene/vinyl acetate copolymer-based adhesives, orthey have a melt viscosity at the application temperature which is toohigh for much of the adhesive application equipment in use today. Itwould therefore be desirable to provide hot melt compositions which havean improved combination of properties with regard to good bond strengthover a wide range of temperatures and low melt viscosity at applicationtemperatures.

SUMMARY OF THE INVENTION In accordance with this invention superiorthermoplas tic adhesive and coating compositions are provided whichcomprise, based on the total thermoplastic components, (A) about 1 to 99percent by weight of thermoplastic segmented copolyester elastomerconsisting essentially of a multiplicity of recurring short chain esterunits and long chain ester units joined through ester linkages, saidshort chain ester units amounting to about 15 to percent by weight ofsaid copolyester and being of the formula and said long chain esterunits amounting to about 25 to percent by weight of said copolyester andbeing of the formula II II --CROOGO-- wherein R is the divalent aromaticradical remaining after removal of the carboxyl groups from aromaticdicarboxylic acid having a molecular weight of less than about 350, D isthe divalent radical remaining after removal of the hydroxyl groups fromorganic diol having a molecular weight of less than about 250, and G isthe divalent radical remaining after removal of the terminal hydroxylgroups from long chain glycol having an average molecular Weight ofabout 350 to 6000, said copolyester having a melt index of less thanabout 150 and a melting point of at least about C., and (B) about 1 to99 percent by weight of low molecular weight thermoplastic resin whichforms compatible mixtures with the segmented copolyester, is thermallystable at C., and has a melt viscosity of less than about 10,000centipoises at 200 C. These compositions are useful as hot melt, heatsealing and pressure sensitive adhesives and coatings.

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic segmentedcopolyester elastomers used in the compositions of this inventionconsist essentially of 15 to 75 percent recurring short chain esterunits and 25 to 85 percent long chain ester units joined through esterlinkages. The term consisting essentially of as used herein, is meant toinclude in the copolyester only those unspecified polymer units which donot materially affect the basic and essential characteristics of thecopolyester as it relates to the compositions of this invention. Inother words, this term excludes unspecified polymeric units in amountswhich prevent the advantages of the compositions of this invention frombeing realized. The term short chain ester units, as applied to units ina polymer chain, refers to the reaction products of low molecular weightdiols with dicarboxylic acids to form repeat units having molecularweights of less than about 550. These units are also referred to hereinas hard segments. The term long chain ester units, as applied to unitsin a polymer chain, refers to the reaction products of long chainglycols with dicarboxylic acids. These units are also referred to hereinas soft segments. Preferably the copolyester consists essentially of 15to 65 percent hard segments and 35 to 85 percent soft segments.

The copolyesters used in accordance with this invention are prepared bypolymerizing with each other (a) one or more aromatic dicarboxylicacids, (b) one or more linear long chain glycols, and (c) one or morelow molecular weight diols. By the term aromatic dicarboxylic acid ismeant a dicarboxylic acid in which each carboxyl group is attached to acarbon atom in an isolated or fused benzene ring or a ring which isitself fused to a benzene ring. The term dicarboxylic acid, as usedherein, is intended to include the equivalents of dicarboxylic acids,that is, their esters or ester-forming derivatives such as acidchlorides and anhydrides, or other derivatives which behavesubstantially like dicarboxylic acids in a polymerization reaction withglycol.

The aromatic dicarboxylic acid monomers useful herein have a molecularweight of less than about 350. This molecular weight requirementpertains to the acid itself and not to its ester or ester-formingderivative. Thus, the ester of a dicarboxylic acid having a molecularweight greater than 350 is included in this invention provided the aciditself has a molecular weight below about 350.

The aromatic dicarboxylic acids used in the preparation of the segmentedcopolyester can contain any substituent groups or combination thereofwhich do not interefere with the polymerization reaction. Representativearomatic dicarboxylic acids include terephthalic acid, isophthalic acid,phthalic acid, dibenzoic acid, substituted dicarboxy compounds withbenzene nuclei such as bis(p-carboxyphenyl) methane,p-oxy(p-carboxyphenyl) benzoic acid, ethylene-bis(p-oxybenzoic acid),ethylene-bis-(p-benzoic acid), tetramethylene-bis(p-oxybenzoic acid),1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid,anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, indenedicarboxylic acid, and the like, as well as ring substituted derivativesthereof such as -0 alkyl, halo, alkoxy or aryl derivatives. Hydroxyacids such as p( 3-hydroxyethoxy) benzoic acid can also be usedproviding an aromatic dicarboxylic acid is also present.

The preferred aromatic dicarboxylic acids for preparation of thesegmented copolyester are the aromatic acids of 8 to 16 carbon atoms,particularly phenylene dicarboxylic acids such as phthalic, terephthalicand isophthalic acids. The most preferred acids are terephthalic acidand mixtures of terephthalic and isophthalic acids.

The low molecular weight diols used in the preparation of the hardsegments of the copolyesters have molecular weights of less than about250. The term low molecular weight diol, as used herein, should beconstrued to include equivalent ester-forming derirvatives. In thiscase, however, the molecular weight requirement pertains to the diolonly and not to its derivatives.

Suitable low molecular weight diols which react to form the short chainester units of the copolyesters include acyclic, alicyclic and aromaticdihydroxy compounds. The preferred diols are those with 2 to carbonatoms such as ethylene, propylene, tetramethylene, isobutylene,pentamethylene, 2,2 dimethyltrimethylene, hexamethylene anddecamethylene glycols, dihydroxy cyclohexane, cyclohexane dimethanol,resorcinol, hydroquinone, 1,5-dihydroxy naphthalene, and the like.Especially preferred are the aliphatic diols of 2 to 8 carbon atoms.Suitable bis-phenols include bis(p-hydroxy diphenyl,bis(p-hydroxyphenyl) methane, bis(p-hydroxyphenyl) ethane,bis(p-hydroxyphenyl) propane and 2,2- bis(p-hydroxyphenyl) propane.Equivalent ester-forming derivatives of diols are also useful. Forexample, ethylene oxide or ethylene carbonate can be used in place ofethylene glycol.

The long chain glycols used to prepare the soft segments of thesecopolyesters have molecular weights of about 350 to 6000, and preferablyabout 600 to 3000. Preferably the long chain glycols have melting pointsof less than about 55 C., and carbon atom to oxygen atom ratios whichare greater than about 2.5, that is, greater than about 2.5 :1. Longchain glycols having carbon to oxygen ratios greater than about 2.5generally have less swell in water and greater resistance to hydrolysis.

The chemical structure of the long chain polymeric part of the longchain glycol is not critical. Any substituent groups which do notinterfere with the polymerization reaction to form the copolyester canbe present. Thus, the chain can be a single divalent acyclic, alicyclic,or aromatic hydrocarbon group, poly (alkylene oxide) group, polyestergroup, a combination thereof, or the like. Any of these groups cancontain substituents which do not interfere to any substantial extentwith the polymerization to form the copolyester used in accordance withthis invention. The hydroxy functional groups of the long chain glycolsused to prepare the copolyesters should be terminal groups to the extentpossible.

Suitable long chain glycols which can be used in preparing the softsegments of the copolymers include poly- (alkylene ether) glycols inwhich the alkylene groups is of 2 to 9 carbon atoms such aspoly(ethylene ether) glycols, poly(l,2- and 1,3-propylene ether) glycol,poly(1,2- butylene ether) glycol, poly(tetramethylene ether) glycol,poly(pentamethylene ether) glycol, polyhexamethylene ether) glycol,poly(heptamethylene ether) glycol, poly(octamethylene ether) glycol,poly(nonamethylene ether) glycol, and random or block copolymersthereof, for example, glycols derived from ethylene oxide and1,2-propylene oxide.

Glycol esters of poly(alkylene oxide) dicarboxylic acids can also beused as the long chain glycol. These glycols may be added to thepolymerization reaction or may be formed in. situ 'by the reaction of adicarboxymethyl acid of poly(alkylene oxide) such as HOOCCH (OCH CH CHCH OCH COOH with the low molecular Weight diol, which is always presentin a stoichiometric excess. The resulting polyalkylene oxide) esterglycol then polymerizes to form G units having the structure present inconsiderable excess.

Polyester glycols can also be used as the long chain glycol. In usingpolyester glycols, care must generally be exercised to control thetendency to interchange during melt polymerization. Certain stericallyhindered polyesters, e.g.,

poly(2,2-dimethyl-1,3-propylene adipate),

poly(2,2-dimethyl-1,3-propylene/2-methyl-2-ethyl-1,3-

propylene 2,S-dimethylterephthalate),

poly(2,2-dimethyl-1,3-propylene/2,2-diethyl-l,3-propylene,

1,4-cyclohexanedicarboxylate and poly(l,2-cyclohexylenedimethylene/2,2-dimethyl-1,3-

propylene, 1,4-cyclohexanedicarboxylate) can be utilized under normalreaction conditions, and other more reactive polyester glycols can beused if proper reaction conditions, including a short residence time,are employed.

Suitable long chain glycols also include polyformals prepared byreacting formaldehyde with glycols such as pentamethylene glycol ormixtures of glycols such as a mixture of tetramethylene andpentamethylene glycols. Polythioether glycols also provide usefulproducts. Polybutadiene and polyisoprene glycols, copolymers of these,and saturated hydrogenation products of these materials are alsosatisfactory long chain polymeric glycols. In addition, the glycolesters of dicarboxylic acids formed by oxidation ofpolyisobutylene-diene copolymers are useful raw materials. The preferredlong chain glycols are poly(alkylene ether) glycols and glycol esters ofpoly(alkylene oxide) dicarboxylic acids.

The relative molecular weight of the segmented copolyester is expressedherein in terms of melt index, which is an empirical measurement ofinverse melt viscosity. The segmented copolyester should have a meltindex of less than about 150 in order to provide useful compositions.The melt indices specified herein are determined by the American Societyfor Testing and Materials (herein abbreviated ASTM) test method D 1238-65T using Condition L at 230 C. with a 2160 gram load.

It is required that the segmented copolyester have a melting point of atleast about 125 C. in order to provide useful compositions. Preferablythe segmented copolyester has a melting point of at least about 140 C.The high melting segmented copolyesters used herein maintain their highmelting characteristics when blended with low molecular weightthermoplastic resins in accordance with this invention.

The required high melting point of the segmented copolyester is obtainedby providing the polyester with crystallizable short chain estersegments. Crystallinity in the short chain ester segments is increasedby the use of more linear and symmetrical aromatic diacid. By lineararomatic diacid is meant a diacid in which each of the bonds between thecarboxyl carbons and their adjacent carbons fall on a straight linedrawn from one carboxyl carbon to the other. By symmetrica aromaticdiacid is meant a diacid which is symmetrical with respect to a centerline drawn from one carboxyl carbon to the other. For example, repeatingester units such as tetramethylene terephthalate give an especially highmelting short chain ester segment. On the other hand, when a non-linearand unsymmetrical aromatic diacid, such as isophthalic acid, is added tocrystallizable short chain ester segments, their melting point isdepressed. Small amounts of isophthalic acid are, however, very usefulfor controlling the melting point and improving the compatibility ofsegmented copolyesters with low molecular weight thermoplastic resins.Aliphatic dibasic acids should be avoided since they give low melting ornon-crystalline short chain ester segments without any significantbeneficial effects.

The melting points specified herein are determined by differentialthermal analysis. The melting point is read from the position of theendotherm peak in a thermogram when the sample is heated from roomtemperature at the rate of C./ min. The details of this method aredescribed in many publications, for example, by C. B. Murphy inDifierential Thermal Analysis, R. C. Mackenzie, Editor, Volume 1, pages643 to 671, Academic Press, New York, 1970.

The preferred segmented copolyester elastomers are those in which thearomatic dicarboxylic acid is of 8 to 16 carbon atoms, the low molecularweight diol is aliphatic diol of 2 to 8 carbon atoms, the long chainglycol is poly(alkylene ether) glycol in which the alkylene group is of2 to 9 carbon atoms, the short chain ester units amount to about 30 to65 percent by weight of the copolyester, the long chain ester unitsamount to about 35 to 70 percent by Weight of the copolyester, and thecopolyester has a melt index of less than about 50 and a melting pointof at least about 140 C.

The copolyester elastomers prepared from terephthalic acid, or a mixtureof terephthalic and isophthalic acids,

l,4-butanediol and polytetramethylene ether glycol having a molecularweight of about 600 to 3000 are particularly preferred in thecompositions of this invention. The raw materials are readily available,and the adhesive and coating properties of compositions obtained fromsuch polymers are outstanding.

A novel class of segmented copolyester elastomers described herein arethose consisting essentially of a multiplicity of recurring short chainester units and long chain ester units joined through ester linkages,said short chain ester units amounting to 15 to less than 30 percent byweight of said copolyester and being of the formula 0 O )R ODO- and saidlong chain ester units amounting to more than to percent by weight ofsaid copolyester and being of the formula 0 O 'iR( }-O GO- wherein R isthe divalent aromatic radical remaining after removal of the carboxylgroups from aromatic dicarboxylic acid having a molecular weight of lessthan 350, D is the divalent radical remaining after removal of thehydroxyl groups from organic diol having a molecular weight of less than250, and G is the divalent radical remaining after removal of theterminal hydroxyl groups from long chain glycol having an averagemolecular weight of 350 to 6000, said copolyester having a melt index ofless than 150, provided that when a polymer in the fiber-formingmolecular weight range formed solely from the total short chain esterunits has a melting point above 200 C., said short chain ester unitsamount to less than 25 percent by weight of said segmented copolyesterelastomer.

The copolyester elastomers used in the compositions of this inventioncan be made by conventional condensation polymerization procedures, asfor example, in bulk or in a solvent medium which dissolves one or moreof the monomers. They are conveniently prepared by a conventional esterinterchange reaction. A preferred procedure involves heating thedimethyl ester of terephthalic acid, or a mixture of terephthalic andisophthalic acids, with a long chain glycol and an excess of a shortchain diol in the presence of a catalyst at to 260 C., followed bydistilling off the methanol formed by the interchange. Heating iscontinued until methanol evolution is complete. Depending on thetemperature, catalyst and diol excess, this polymerization is completewithin a few minutes to a few hours. This procedure results in thepreparation of a low molecular weight prepolymer which can be convertedto the high molecular weight segmented copolyester used in thecompositions of this invention.

These prepolymers can also be prepared by a number of alternateesterification or ester interchange processes. For example, the longchain glycol can be reacted with a high or low molecular weight shortchain ester homopolymer or copolymer in the presence of catalyst untilrandomization occurs. The short chain ester homopolymer or copolymer canbe prepared by ester interchange from either the dimethyl esters and lowmolecular weight diols, as above, or from the free acids with the diolacetates. Alternatively, the short chain ester copolymer can be preparedby direct esterification from appropriate diacids, anhydrides or acidchlorides, for example, with diols or by other processes such asreaction of the diacids with cyclic ethers or carbonates. Obviously theprepolymer can also be prepared by carrying out these processes in thepresence of the long chain glycol.

The resulting prepolymer is then converted to the high molecular weightsegmented copolyester elastomer by distillation of the excess of shortchain diol. Best results are usually obtained if this final distillationis carried out at less than 1 mm. pressure and 240-260 C. for less than2 hours in the presence of an antioxidant such assym-dibeta-naphthyl-p-phenylenediamine or 1,3,5-trimethyl-2,4,6-tris[3,5-ditertiary-butyl-4-hydroxybenzyl] benzene.

Most practical polymerization techniques rely upon ester interchange tocomplete the polymerization reaction. In order to avoid excess holdtimes at high temperatures with possible irreversible thermaldegradation, it is advantageous to employ a catalyst for the esterinterchange reaction. While a wide variety of catalysts can be used,organic titanates such as tetrabutyl titanate, used alone or incombination with magnesium or zinc acetates, are preferred. Complextitanates, such as derived from alkali or alkaline earth metal alkoxidesand titanate esters are also very effective. Inorganic titanates such aslanthanum titanate, calcium acetate/antimony trioxide mixtures andlithium and magnesium alkoxides are representative of other catalystswhich can be used.

While these condensation polymerizations are generally run in the meltwithout added solvent, it is sometimes advantageous to run them in thepresence of inert solvent in order to facilitate removal of volatileproducts at lower than usual temperatures. This technique is especiallyvaluable during prepolymer preparation, for example, by directesterification. However, certain low molecular weight diols, forexample, butanediol in terphenyl, are conveniently removed during highpolymerization by azeotropic distillation. Other special polymerizationtechniques, for example, interfacial polymerization of bisphenol withbisacylhalides and bisacylhalide capped linear diols, may prove usefulfor preparation of specific polymers.

The processes described above can be run both by batch and continuousmethods. The preferred method for continuous polymerization, namely,ester interchange with a prepolymer, is a well established commercialprocess.

In addition to the segmented copolyester, the compositions of thisinvention also contain one or more low molecular weight thermoplasticresins which form compatible mixtures with the segmented copolyester,are thermally stable at about 150 C., and have melt viscosities of lessthan about 10,000 centipoises at 200 C. The term thermoplastic resin, asused throughout the specification and claims, is intended to includeheat softenable resins, both natural and synthetic, as well as waxytypes of materials. By the term compatible it is meant that there is noseparation into distinct layers between the segmented copolyester andthe low molecular weight resin or resins at the copolyester melttemperature. In some cases this compatibility is achieved inmulti-component blends even though one of the low molecular weightthermoplastic resin components may not be compatible with the segmentedcopolyester elastomer alone, By the phrase thermally stable, it is meantthat there is no significant permanent alteration in the properties ofthe resin after heating at the specified temperature 'for one hour inthe presence of air. The melt viscosities specified herein are measuredwith a Brookfield viscometer by ASTM test method D1824-66 at elevatedtemperatures as indicated.

Suitable low molecular weight thermoplastic resins include hydrocarbonresins, bituminous asphalts, coal tar pitches, rosins, phenolic resins,chlorinated aliphatic hydrocarbon waxes, chlorinated polynucleararomatic hydrocarbons, and the like.

The term hydrocarbon resins refers to hydrocarbon polymers derived fromcoke-oven gas, coal-tar fractions, cracked and deeply cracked petroleumstocks, essentially pure hydrocarbon feeds, and turpentines. Typicalhydrocarbon resins include coumarone-indene resins, petroleum resins,styrene polymers, cyclopentadiene resins, and terpene resins. Theseresins are fully described in the Kirk-Othmer Encyclopedia of ChemicalTechnology,

8 Second Edition, 1966, Interscience Publishers, New York. Volume 11,Pages 242 to 255.

The term coumarone-indene resins refers to hydrocarbon resins obtainedby polymerization of the resin formers recovered from coke-oven gas andin the distillation of coal tar and derivatives thereof such asphenolmodified coumarone-indene resins. These resins are fully describedin the Kirk-Othmer Encyclopedia, supra, Volume 11, Pages 243 to 247.

The term petroleum resins refers to hydrocarbon resins obtained by thecatalytic polymerization of deeply cracked petroleum stocks. Thesepetroleum stocks generally contain mixtures of resin formers such asstyrene, methyl styrene, vinyl toluene, indene, methyl indene,butadiene, isoprene, piperylene and pentylenes. These resins are fullydescribed in the Kirk-Othmer Encyclopedia, supra, Volume 11, Pages 248to 250. The so-called polyalkylaromatic resins fall into thisclassification.

The term styrene polymers refers to low molecular weight homopolymers ofstyrene as well as copolymers containing styrene and other comonomerssuch as alphamethyl-styrene, vinyl toluene, butadiene, and the like whenprepared from substantially pure monomer.

The term cyclopentadiene resins refers to cyclopentadiene homopolymersand copolymers derived from coal tar fractions or from cracked petroleumstreams. These resins are produced by holding acyclopentadienecontaining stock at elevated temperature for an extendedperiod of time. The temperatures at which it is held determines whetherthe dimer, trimer, or higher polymer is obtained. These resins are fullydescribed in the Kirk- Othmer Encyclopedia, supra, Volume 11, Pages 250and 251.

The term terpene resins refers to polymers of terpenes which arehydrocarbons of the general formula 0 1-1 occurring in most essentialoils and oleoresins of plants, and phenol-modified terpene resins.Suitable terpenes include alpha-pinene, beta-pinene, dipentene,limonene, myrcene, bornylene, camphene, and the like. These productsoccur as by-products of coking operations of petroleum refining and ofpaper manufacture. These resins are fully described in the Kirk-OthmerEncyclopedia, supra, Volume 11, Pages 252 and 254.

The term bituminous asphalts is intended to include both native asphaltsand asphaltites such as Gilsonite, Glance pitch and Grahanite. A fulldescription of bituminous asphalts can be found in Abrahams Asphalts andAllied Substances, 6th Edition, Volume 1, Chapter 2, Van Nostrand Co.,Inc., particularly Table III on Page 60.

The term coal tar pitches refers to the residues obtained by the partialevaporation or distillation of coal tar obtained by removal of gaseouscomponents from bituminous coal. 'Such pitches include gas-works coaltar pitch, coke-oven coal tar pitch, blast-furnace coal tar pitch,producer-gas coal tar pitch, and the like. These pitches are fullydescribed in Abrahams Asphalts and Allied Substances, supra,particularly Table II'I on Page 61.

The term rosins refers to the resinous materials that occur naturally inthe oleoresin of pine trees, as well as derivatives thereof includingrosin esters, modified rosins such as fractionated, hydrogenated,dehydrogenated and polymerized rosins, modified rosin esters, and thelike. These materials are fully described in the Kirk-OthmerEncyclopedia, supra, Volume 17, Pages 475 to 505.

The term phenolic resins refers to the products resulting from thereaction of phenols with aldehydes. In addition to phenol itself,cresols, xylenols, p-tert.-butyl phenol, p-phenylphenol and the like maybe used as the phenol component. Formaldehyde is the most commonaldehyde, but acetaldehyde, furfuraldehyde and the like may also beused. These resins are fully described in the 9 Kirk-OthmerEncyclopedia, supra, Volume 15, Pages 176 to 207.

The term chlorinated aliphatic hydrocarbon waxes refers to those waxeswhich are commonly called chlorinated waxes such as chlorinated parafiinwaxes. These waxes typically contain about 30-70 percent by weight ofchlorine.

The term chlorinated polynuclear aromatic hydrocarbons refers tochlorinated aromatic hydrocarbons containing two or more aromatic ringssuch as chlorinated biphenyls, terphenyls, and the like, and mixturesthereof. These materials typically contain 30 to 70 percent by Weight ofchlorine.

The compositions of this invention contain about 1 to 99 percent byweight of thermoplastic segmented copolyester elastomer and about 1 to99 percent by weight of low molecular weight thermoplastic resin.Preferably, the composition contains about to 95 percent by weight ofthermoplastic segmented copolyester elastomer and about 5 to 95 percentby weight of low molecular weight thermoplastic resin.

Typically the compositions of this invention contain more than one lowmolecular weight thermoplastic resin. For example, low molecular weightstyrene polymers have been found to lower the melt viscosity of thesecompositions without substantially lowering the softening point. Sincelow melt viscosity contributes improved wetting by the composition ofthe surface of the substrate, which results in better adhesion, manyuseful compositions will contain some styrene polymer. Styrene polymersare also useful for increasing the compatibility of other resins withthe segmented copolyester elastomer. Coumarone-indene resins of highsoftening point have been found to give strength to the compositions.Phenol-modified coumaroneindene resins have been found to have theeffect of lowering the softening point of the compositions. In fact, theeffect of phenol-modified coumarone-indene resins on the melting pointis so great that the desired melting point is generally achieved by theaddition of only a small amount of this resin. Any combination of thesedesired properties can be achieved by mixing two or more low molecularweight thermoplastic resins with the copolyester elastomer in a properproportion.

A particularly preferred composition contains segmented copolyesterelastomer, styrene polymer, and one or more additional low molecularweight thermoplastic resin. The additional low molecular weightthermoplastic resins also have the effect of lowering the cost of thecomposition.

It is sometimes desirable to stabilize the compositions of thisinvention against heat or radiation by ultra-violet light. This can bedone by incorporating stabilizers or antioxidants in these compositions.Satisfactory stabilizers comprise phenols and their derivatives, aminesand their derivatives, compounds containing both hydroxyl and aminegroups, hydroxyazines, oximes, polymeric phenolic esters, and salts ofmultivalent metals in which the metal is in its lower valence state.

Representative phenol derivatives useful as stabilizers includehydroquinone,

2,6-ditertiary-butyl-p-cresol,

tetrakis [methylene-3 (3 5 -ditertiary-butyl-4'-hydroxyphenyl)propionate] methane,

4,4-bis( 2,6-ditertiary-butylphenol) 1,3,5 -trimethyl-2,4-tris [3 ,5-ditertiary-butyl-4-hydroxybenzyl] benzene, and

4,4'-butylidene-bis( 6-tertiary-butyl-m-cresol) Various inorganic metalsalts or hydroxides can be used as well as organic complexes such asnickel dibutyl dithiocarbamate, manganous salicylate, and copper3-phenylsalicylate. Typical amine stabilizers include aromatic aminessuch as N,N' bis(beta-naphthyl)-p-phenylenediamine, N,Nbis(l-methylheptyl)-p-phenylene diamine,

and either phenyl-beta-naphthyl amine or its reaction products withaldehydes. Mixtures of hindered phenols with esters of thiodipropionicacid, mercaptides and phosphite esters are particularly useful.Additional stabilization to ultraviolet light can be obtained bycompounding with various UV absorbers such as substituted benzophenonesor benzotriazoles.

The properties of the compositions of this invention can be modified bythe incorporation of various conventional inorganic fillers such as woodflour, silicates, silica gel, alumina, clays, chopped fiber glass,titanium dioxide, carbon black, and the like. In general, fillers havethe effect of increasing the melt viscosity and the modulus or stiffnessof the composition at various elongations.

The properties of the compositions of this invention can be furthermodified by the incorporation of thermally stable thermoplastic polymersof ethylenically unsaturated monomers including homopolymers of vinylesters such as vinyl acetate, copolymers of these vinyl esters withother vinyl monomers such as ethylene, vinyl chloride and the like, andpolymers of alkyl acrylates and methacrylates, or thermally stablecondensation polymers such as polyesters and polyamides, and the like.For example, the addition of a copolymer of ethylene and vinyl acetateoften increases the tackiness of pressure sensitive adhesivecompositions of this invention. These modifying polymers typically havemelt viscosities above about 10,000 centipoises at 200 C. and thus arenot low molecular weight thermoplastic resins as defined herein.

These compositions can also be colored by the addition of organic orinorganic pigments or organic dyes where their effect is desired.Suitable inorganic pigments include rutile and anatase titaniumdioxides, aluminum powder, cadmium sulfides and sulfo-selenides, leadantimonate, mercury cadmiums, chromates of nickel, tin and lead, ceramicgreens such as chromium, cobalt, titanium and nickel oxides, ceramicblacks such as chromium, cobalt and iron oxides, carbon black,ultramarine blue, and the like. Suitable organic pigments includephthalocyanine blues and greens, quinacridones, and the like. Suitabledyes include disperse dyes such as Colour Index Disperse Blues 59, 63and 64. Optical brightness such as Uvitex CF, sold by Ciba Corp., andTinopal AN, sold by Geigy Chemical Corp., may also be incorporated wheretheir effect is desired.

Plasticizers including phthalate esters such as dioctyl phthalate, andaryl phosphates such as tricresyl phos phate, and the like, may be addedfor applications where their effect is desired. Flame retardantadditives, such as zinc borate, antimony trioxide,tris(2,3-dichloropropyl) phosphate, tris(2,3 dibromopropyl) phosphate,chlorinated waxes, and the like may be added, if desired. Other minoradditives such as surfactants or lubricants may also be added.

One of the important advantages of the thermoplastic compositions ofthis invention is that the copolyester elastomers and the low molecularweight thermoplastic resins are easy to blend together due to therelatively low melt viscosity of these compositions at elevatedtemperatures as compared to compositions of the prior art havingcomparable bond strength. The components of the compositions of thisinvention can be blended by variously well known procedures such as, forexample, blending in molten form, blending in a solvent, or mixingaqueous dispersions of the components. Blending in the melt may becarried out by first melting the segmented copolyester elastomer andthen adding low molecular weight thermoplastic resin to the melt, byfirst melting the low molecular weight thermoplastic resin and thenadding segmented copolyester elastomer to the melt, or by first blendingthe segmented copolyester elastomer and the low molecular weightthermoplastic resin together in finely divided form and then melting theblend, for example, on a hot roller mill or by simultaneously feedingthe components to an extruder.

In addition to these blending procedures, it is also possible to takethe copolyester from the synthesis step and, while it is still molten,blend solid, premelted, or liquid low molecular weight thermoplasticresin with it. Other ingredients such as antioxidants, fillers,plasticizers, and the like can also be added at this time. This blendingprocess can be carried out with an in-line mixer or with a separatemixing vessel, and has the advantage that it does not require isolationof the copolyester.

The thermoplastic compositions of this invention can also be blended bydissolving the segmented copolyester and the low molecular weightthermoplastic resin in a solvent. Suitable solvents for preparing thesesolutions include chlorinated hydrocarbons such as methylene chloride,chloroform, trichloroethylene, solvent mixtures such as mixtures oftrichloroethylene and isopropanol, and the like.

Aqueous dispersions of the thermoplastic compositions of this inventioncan be prepared by dissolving the segmented copolyester and the lowmolecular weight thermoplastic resin together in a suitablewater-immiscible organic solvent, emulsifying the organic solventcontaining the segmented copolyester and the low molecular weightthermoplastic resin in Water, and removing the organic solvent asdescribed by Funck and Wolff in US. Pat. No. 3,296,172. Dispersions canalso be prepared by dissolving the segmented copolyester in a suitablewater-immiscible organic solvent, dissolving the low molecular weightthermoplastic resin in a different water-immiscible organic solvent,emulsifying each organic solvent solution in Water, removing the organicsolvent from each emulsion, thereby forming separate dispersions, andmixing the dispersions together in proper amounts.

The compositions of this invention are useful as adhesives and ascoating compositions. These compositions can be applied in the form of adry \blend, a solution, an aqueous dispersion, or in molten form. Themethod of application does not appreciably affect the performance ofthecomposition.

Conventional application equipment can be used for applying thecompositions of this invention in the various forms. For application ofsolutions or dispersions, as in the case of heat sealing and pressuresensitive adhesives, various known application techniques can be usedincluding brushing, dipping, roll coating, wire-wound rod application,doctoring, printing, and the like. Spraying or curtain coatingtechniques are also applicable to these forms of the compositions.

For application of these compositions in the melt form, dipping, rollcoating, calendering, curtain coating, extruding, hot spraying, andother hot melt application techniques can be used. Powder coatings ofappropriate nontacky compositions can also be applied by known fluidizedbed techniques, electrostatic powder spray application, or plasmaspraying.

In using the compositions of this invention as hot melt adhesives, thejoining step can be accomplished by applying the molten composition toone surface, bringing the other surface into contact with the moltencomposition, and allowing the bond to cool. Coatings of thesecompositions can be bonded to other surfaces or themselves by heat orsolvent activation of the coating, and contacting the activated coatingwith the second surface and allowing the bond to cool or the solvent toevaporate. Heat activation of the coating is typically carried out in anoven or using an infrared lamp. Simultaneous application of heat andpressure, or heat sealing, can be used with these compositions toaccomplish bonding. High frequency dielectric and ultrasonic waves canalso be used to activate these compositions to effect bonding.

The compositions of this invention are characterized by an outstandingcombination of properties. These com positions have demonstratedexcellent adhesion to many substrates including difficulty adherablesubstrates such as polypropylene. The compositions containing up to 50percent by weight of segmented copolyester typically have 180 peelstrengths higher than about 0.2 pounds per linear inch with a variety ofsubstrates. They have high temperature bond strengths, for example, asshown by failure temperatures higher than about 70 C. in the WPS68 test.They have good low temperature flexibility. that is, resistance tobreakage on impact, and a minimum elongation of 50 percent at roomtemperature. They have sufiicient thermal stability to render themsuitable for hot melt application with good pot life. Heating to 150 to200 C. does not appreciably alter the properties of the composition.They also have tensile strengths higher than 200 psi. at roomtemperature.

The compositions containing up to 50 percent by Weight of segmentedcopolyester elastomer are particularly useful as hot melt adhesives in aWide variety of adhesive use applications such as edge banding andsurface lamination, for example, in furniture manufacture, vinyllamination, sole attachment and box-toe construction in shoe assembly,and as pressure sensitive adhesives for carpet tiles, vinyl tiles,premium labels, tapes, decals, decorative molding of wood or plastic,and the like.

Compositions containing about 50 percent or more by weight ofthermoplastic segmented copolyester elastomer are particularly useful inthe preparation of molded, extruded, and dipped goods, coatings,binders, extruded adhesives, sealants, and the like. "Films can beprepared from these compositions by molding, extrusion and calenderingtechniques. These compositions typically contain about 50 to 99 percentby weight segmented copolyester elastomer and about 1 to 50 percent byweight of low molecular weight thermoplastic resin. Preferably theycontain about 50 to percent by Weight of segmented copolyester elastomerand about 5 to 50 percent by Weight of low molecular weightthermoplastic resin.

Compositions containing these higher concentrations of segmentedcopolyester elastomer can also be used as concentrates for furthercompounding with the same or other low molecular weight thermoplasticresins and modifiers, as well as being useful as such. Such concentratedcompositions have the advantage of being processable with additionalcomponents at lower temperatures and shear requirements than thesegmented copolyester elastomer itself. For example, a mixturecontaining an equal weight of segmented copolyester elastomer and lowmolecular weight, thermoplastic styrene homopolymer is typically blendedat a minimum temperature of about 170 C. However, additional lowmolecular weight thermoplastic resins can be mixed with this concentrateat a minimum blending temperature of about C. Moreover, additional lowmolecular weight thermoplastic resins which have limited compatibilitywith the segmented copolyester elastomer alone tend to be morecompatible With such concentrates.

The addition of small amounts of lower melting thermoplastic resins tothermoplastic segmented copolyester com positions improves the adhesionof these compositions to reinforcement components in the manufacture ofrubber articles such as fabric reinforced flexible belting and hose, andcoated fabrics. For example, blends containing 90 percent thermoplasticsegmented copolyester with 5 percent polystyrene resin and 5 percentcoumarone-indene resin have very desirable wetting characteristics withgood penetration into woven and non-Woven fabrics resulting in highmechanical adhesion. In many cases, these effects can be achieved atrelatively low application temperatures thereby protecting the fabriccomponents from extensive heat damage. These compositions are alsouseful as binders in thread and cord manufacture.

The compositions of this invention are particularly useful in themanufacture of reinforced flexible hose. Hoses are conventionallyprepared by placing a braid, spiral, wrapped ply, loom or knitreinforcement layer over a suitable polymeric inner tube. Thereinforcement layer may be made of cotton, synthetic yarn or wire.

Adhesion of the reinforcement layer is usually obtained by impregnatingthe reinforcement layer with a binder, that is, a thin layer of gum,called friction, or a dough or cement composition. An outer cover layerof a suitable polymeric material is then applied. Binder layers aregenerally applied from a solvent-containing coating composition followedby a drying step to remove the solvent. Cover layers are generallyapplied by cross-head extrusion.

Use of the compositions of this invention in the manufacture ofreinforced flexible hose has led to the development of new and improvedmanufacturing techniques. Because of their improved rheologicalproperties, particularly their low melt viscosity, the compositions ofthis invention, when used as a cover layer, give improved processingbehavior in conventional cross-head extrusion operations. The uniquewetting properties of these compositions allow improved penetration intoand adhesion to the reinforcement layer.

Moreover, these compositions can be used as a solventfree hot meltbinder for the reinforcement layer, thereby eliminating the drying stepto drive off solvent. The hot melt binder may be applied in thereinforcement layer using hot melt techniques such as drawing the innertube with an unimpregnated reinforcement layer through a funnelapplicator.

Furthermore, the unique rheological, wetting and adhesive properties ofthe compositions of this invention allow one to apply a cover layer ofthese compositions to the unimpregnated reinforcement layer without anyadverse eifect from the absence of the binder. These compositions can beapplied by hot melt techniques such as by drawing the inner tube with anunimpregnated reinforcement layer through a funnel applicator having anexit orifice corresponding to the desired outside diameter of thefinished hose. When applying these compositions in this novel manner,process simplification and reduced equipment investment are achieved ascompared with a conventional two-step process involving solution coatingwith a binder followed by cross-head extrusion of the cover layer.

When the compositions of this invention are used in the manufacture ofreinforced flexible hose, the composition may vary over the range ofabout 1 to 99 percent by weight of segmented copolyester and about 1 to99 percent by weight of low molecular weight thermoplastic resin.Compositions which are applied in a separate step in the binder layerpreferably contain about 5 to 50 percent by weight of segmentedcopolyester and about 50 to 95 percent by weight of low molecular weightthemoplastic resin. When the composition is used as the cover layer, oras the binder and cover layers in a single step, it preferably containsabout 50 to 95 percent by weight of segmented copolyester and about 5 to50 percent by weight of low molecular weight thermoplastic resin.

EXAMPLES OF THE INVENTION The following examples, illustrating the noveladhesive and coating compositions of this invention, are given withoutany intention that the invention be limited thereto. All parts andpercentages are by weight.

In the examples, ring and ball softening points of the blends weredetermined by ASTM test method E28-67. Tensile properties weredetermined with compression molded samples using ASTM test methodD1708-66. The peel strengths of the segmented copolyester-basedadhesives of this invention were determined in the examples by a 180peel test using a plastic film laminated to a particle board inaccordance with ASTM test method D903-49.

High temperature bond failure temperatures were determined by testmethod WPS-68 described by W. Schneider and D. Fabricius in the Germanperiodical Adhaesion, January 1969, Pages 28-37. This test measures thetemperature at which the bond between a particle board and wood veneeror plastic band fails under a constant shear stress of g./cm. when theenvironmental temperature is raised by a 5 C. increment every hour.

Example 1 In a 500 ml. resin kettle were placed 195 g. of Piccolastic A50, a low molecular weight styrene homopolymer having a softening pointof 50 C. and a melt viscosity of 29 centipoises at 190 C. sold byPennsylvania Industrial Chemical Corp., and 1.5 g. of Irganox 1010, atetrakis[methylene 3 (3',5 di t butyl 4 hydroxyphenyl) propionate]methane high melting phenolic antioxidant sold by Geigy Chemical Co.,and the contents were heated to 175 C. in an oil bath. To the moltenmixture was added g. of a segmented copolyester derived 35.4% fromterephthalic acid, 13.4% from butanediol and 51.2% frompoly(tetramethylene ether) glycol (abbreviated PTMEG hereafter) having amolecular weight of about 1000, containing 42.6 percent short chainester units and having a melting point of C. measured by differentialthermal analysis and a melt index of 47.7, while stirring at C. Themixing was continued for 2 hours at 175 C. under a continuous slowstream of nitrogen to give a transparent mixture which on cooling toroom temperature became an opaque, slightly tacky, rubbery material. Theblend had a melt viscosity of 8400 cps. at 190 C., showed strongadhesion to various plastic substrates, had a ring and ball softeningpoint of 154 C., a high temperature bond failure temperature of 130-135C., a tensile strength of 800 p.s.i., and an elongation of 1100%.

Example 2 On a roller mill heated to C. was placed 12 g. of a segmentedcopolyester derived 28.6% from terephthalic acid, 9.3% from butanedioland 62.1% from PTMEG having a molecular weight of about 1000, containing29.8% short chain ester units, and having a melting point of 149 C. anda melt index of 18. To the molten copolyester were added 28 g. of Foral10.5, a pentaerythritol ester of a stabilized rosin having a ring andball softening point of 105 C. sold by Hercules, Inc., and 0.4 g. ofIrganox 1010 antioxidant (Example 1). After about 10 minutes of millingat 185 C., a homogeneous mixture was obtained. This blend was used as anadhesive between a particle board and a strip of Formica, a highpressure melamine/formaldehyde laminate. The adhesive had a hightemperature bond failure temperature of 110-115 C.

Example 3 In the same manner as in Example 2, 24 g. of Foral 105 rosinester (Example 2), 16 g. of a segmented copolyester derived 29.2% fromterephthalic acid, 12.2% from butanediol, and 58.6% from PTMEG having amolecular weight of about 2100, containing 38.0% short chain esterunits, and having a melting point of 188 C. and a melt index of 89, and0.4 g. of Irganox 1010 antioxidant (Example 1) were blended. Thecomposition had a high temperature bond failure temperature above 150 C.

Example 4 To a A: gallon sigma-blade mixer heated by high pressure steamto 170 C. were charged 0.6 lb. of Piccoumaron 410 HL, a polyindene type,highly aromatic, thermoplastic petroleum resin having ring and ballsoftening point of about 110 C. and a melt viscosity of 158 centipoisesat 190 C. sold by Pennsylvania Industrial Chemical Corp., 0.6 lb. ofPiccolastic A 5, a low molecular weight styrene homopolymer having ringand ball softening point of about 5 C. and a melt viscosity of 18centipoises at 190 C. sold by Pennsylvania Industrial Chemical Corp.,and 0.01 lb. of Irganox 1010 antioxidant (Example 1). To the abovemolten mixture was added 0.8 lb. of a segmented copolyester derived31.6% from terephthalic acid, 9.2% from isophthalic acid, 16.6% frombutanediol, and 42.6% from PTMEG having a molecular weight of about1000, containing 52.6% short chain ester units, and having a meltingpoint of 158 C. and a melt index of 15. The mixing was continued for 1hour and 45 minutes at 170 C. after which the mixture was homogeneous.The blend had a melt viscosity of 30,000 cps. at 190 C., and the hightemperature bond failure temperature of a Formico/particle board bondwas 130135 C. The 180 peel strengths were 20 pounds per linear inch(p.l.i.) to Decatone, a plasticized polyvinyl chloride film back-printedwith a wood grain pattern sold by Litton Indusries, 30 p.l.i. to plainpolyvinyl chloride film, and 20 p.l.i. to Mylar, a polyethyleneterephthalate polyester film sold by E. I. du Pont de Nemours and Co.,Inc. These values compare favorably with commercially availableadhesives which typically give less than about 5 p.l.i. peel strength.The blend showed a tensile strength of 1,100 p.s.i. and an elongation ofl,200%.

Formica laminate strips were bonded to edges of particle boards with theabove adhesive composition using a Raimann Edge Bander, an automaticedge banding machine, at a machine speed of 55-60 feet/ min. and anadhesive temperature of about 200 C. The edge-banded particle boarddeveloped no defects during an accelerated high temperature test at 82C. for 19 hours.

Similarly, walnut veneer strips were edge-banded to particle boards. Oilstain and a lacquer finish Were applied, followed by high temperaturedrying, all of which had no adverse effect on the tight bond obtained.

Example 5 In the same manner as Example 1, 93 g. of Piccolastic A 5styrene homopolymer (Example 4), 90 g. of Piccoumaron 410 HL polyindenepetroleum resin (Example 4), 1.5 g. of Irganox 1010 antioxidant (Example1), and 120 g. of a segmented copolyester were blended, except that theoil bath temperature was 210 C. The copolyester was derived 44.4% fromterephthalic acid, 18.8% from butanediol, and 36.8% from PTMEG having amolecular weight of 1000, contained 59.3% short chain ester units, andhad a melting point of 203 C. and a melt index of 8. The ring and ballsoftening point of the blend was above 180 C. The blend adhered stronglyto Formica when applied in molten form at 200 C.

Example 6 In the same manner as in Example 2, a well mixed blend wasprepared from 20 g. of segmented copolyester derived 31.1% fromterephthalic acid, 16.7% from isophthalic acid, 21.0% from butanediol,and 31.2% from PTMEG having a molecular weight of about 1,000,containing 65.6% short chain ester units, and having a melting point of137 C. and a melt index of 7, 22.5 g. of Piccoumaron 410 HL polyindenepetroleum resin (Example 4), 7.5 g. of Piccolastic A 5 styrenehomopolymer (Example 4), and 0.25 g. of Irganox 1010 antioxidant(Example 1). The blend had a tensile strength of 2300 p.s.i. and anelongation of 810%. When a =Formica strip was bonded to a particle boardusing this composition as a hot melt adhesive, a strong and tight jointwas obtained. The high temperature bond failure temperature was 130-135C.

Example 7 The segmented copolyester used in Example 4 was mixed in theratio of 4:6 with Piccournaron 10, a polyindene type, highly aromatic,thermoplastic petroleum resin having a ring and ball softening point ofC. and a melt viscosity of 40 centipoises at 190 C. sold by PennsylvaniaIndustrial Chemical Corp. The blend had the melt viscosity of 27,000cps. at 190 C., and a high temperature bond failure temperature of135l40 C. in a -Formica/particle board bond.

Example 8 The segmented copolyester used in Example 4 and Neville R-27,a coumarone-indene resin having a ring TABLE I 180 peel strength, p.l.i.to- Softening point, Deea- Modifying resin 0 tone PVC Mylar Neville R-27139 18 22 13 "N evillao 10 69 18 18 5 'Example 9 The segmentedcopolyester used in Example 4 and LTP 115, a phenol-modified terpeneresin having a softening point of C. and a melt viscosity of 224centipoises at 190 C. sold by Pennsylvania Industrial Chemical Corp.,were blended in a ratio of 3:7 in the manner described in Example 1. Ahard resinous blend was obtained. Its adhesive properties were improvedby replacing 40% of the LTP 115 with Piccolastic A 5 styrene homopolymer(Example 4). The ternary blend thus obtained was tough and flexible andshowed peel strengths of 17 p.l.i. to Decatone film (Example 4) and 26p.l.i. to Mylar film (Example 4).

Example 10 Intimate blends of the segmented copolyester used in Example4 and Piccolastic A 5 styrene homopolymer (Example 4) were prepared bythe procedure described in Example 1. Highly adhesive, elastomericblends were obtained. Some properties of the blends are shown in TableII. Small amounts of the segmented copolyester markedly increase thesoftening point of the Piccolastic A 5 resin.

TABLE II Melt 180 peel strength, viseos- R and B p.l.i. t0

ity at softening Copolyester/ 190 C point, "Deca- "Piceolastic A5 cps. 0tone PVC Mylar Example 11 In the same manner as in Example 2, 16 g. ofthe segmented copolyester of Example 4, 16 g. of Durez 12603, athermoplastic, oil soluble, terpene phenolic resin having an averagering and ball softening point of 152 C. sold by Hooker Chemical Corp., 8g. of Piccolastic A 5 styrene homopolymer (Example 4) and 0.2 g. ofIrganox 1010 antioxidant (Example 1) were thoroughly mixed. The productwas a nearly transparent tough adhesive, which showed a bond failuretemperature of 115 to 120 C. A product of similar properties wasprepared by using CKM 2432, a thermoplastic, oil soluble, phenolic resinsold by Union Carbide Corp. in place of the Durez" resin.

Example 12 A blend consisting of 40 g. of the segmented copolyester ofExample 4, 40 g. of Piccoumaron 410 HL polyindene petroleum resin(Example 4), 20 g. of tricresyl phosphate plasticizer and 0.5 g. ofIrganox 1010 antioxidant (Example 1) was prepared in the same manner asin Example 1. The product was non-tacky and highly flexible and had ahigh temperature bond failure temperature of 120 to C.

17 Example 13 In the same manner as in Example 2, 16 g. of a segmentedcopolyester derived 31.6% from terephthalic acid, 9.2% from isophthalicacid, 16.6% from butanediol and 42.6% from Carbowax 1000, apoly(ethylene ether) glycol having a molecular weight of about 1000 soldby Union Carbide Corp, containing 52.5% short chain ester units, andhaving a melting point of 140 C. and a melt index of 24, 12 g. ofNevindene R-7, a coumaronindene resin having a ring and ball softeningpoint of 93-- 120 C. sold by Neville Chemical Co.. 12 g. of Neville R 27coumarone-indene resin (Example 8), and 0.2 g. of Irganox 1010antioxidant (Example 1) were thoroughly mixed. The resulting blend was agood adhesive, e.g., the bond strength of Decatone polyvinyl chloridefilm (Example 4) bonded to particle boards with this material was 7 to12 lbs/in. when peeled at 180 angle at a rate of 0.2 in./min. The blendhad a tensile strength of 1160 p.s.i. and an elongation of 1200% atbreak.

Example 14 In the same manner as in Example 1, 40 g. of a segmentedcopolyester derived 29.7% from terephthalic acid, 7.4% from isophthalicacid, 16.4% from butanediol and 46.5% from Voranol P-2001, an ethyleneoxide capped poly(1,2-propylene ether) glycol of molecular weight ofabout 2000 sold by Dow Chemical Co., containing 51.0% short chain esterunits, and having multiple melting points of 169 C., 183.5 C. and 191C., and a melt index of 5.2, 20 g. of LTP 115 phenol-modified terpeneresin (Example 9), 40 g. of Piccoumaron polyindene petroleum resin(Example 7) and 0.5 g. of Irganox 1010 antioxidant (Example 1) wereblended. The product was a strong adhesive which gave a substratetearing bond when Decatone was laminated on the surface of particleboards.

Example 15 In the same manner as in Example 4, parts of the segmentedcopolyester used in Example 4, 55 parts of Piccolastic A 5 styrenehomopolymer (Example 4), parts of LTP 115 terpene resin (Example 9), and0.5 part of Irganox 1010 antioxidant (Example 1) were blended. The blendwas a pressure sensitive adhesive with good peel-reseal properties.

Example 16 By the method described in Example 2, 12 g. of the segmentedcopolyester used in Example 4, and 28 g. of Aroclor 5460, a chlorinatedpolyphenyl available from Monsanto Co., were blended on a hot rollermill. The homogeneous mixture obtained had a softening temperature of116 C. and showed peel strengths of 11 p.l.i. t0 Decatone film (Example4), and 36 p.l.i. to standard polyvinyl chloride film.

Example 17 In the same manner as in Example 1, 20 parts of the segmentedcopolyester used in Example 4, 60 parts of Piccolastic A 5 styrenehomopolymer (Example 4), 20 parts of Elvax 150, and ethylene/vinylacetate copolymer containing 33% vinyl acetate sold by E. I. du Pont deNemours and Co., Inc., and 0.5 part of Irganox" 1010 antioxidant(Example 1) were thoroughly mixed. The blend had a ring and ballsoftening point of 152 C., but maintained tackiness for a few hoursafter the molten blend was allowed to cool at room temperature.

Example 18 In the manner described in Example 2, parts of the segmentedcopolyester described in Example 4, and 70 parts of Transphalt 50, abituminous asphalt having ring and ball softening point of 50 C.available from Pennsylvania Industrial Chemical Corp., and 0.5 part ofIrganox 1010 antioxidant (Example 1) were blended into an inti- 18 matemixture. The heat seal bond between Decatone" films with this mixturegave a 180 peel strength of 11 p.l.i.

Examples 19-24 Using a 1000 ml. resin kettle, the segmented copolyesterelastomer of Example 3 was blended with various amounts of LTP terpeneresin (Example 9); Piccolastic A 5 styrene homopolymer (Example 4);Piccolastic A 25, a low molecular weight styrene homopolymer having aring and ball softening point of about 25 C. sold by PennsylvaniaIndustrial Chemical Corp, Nevillac Hard, a phenol-modifiedcoumarone-indene thermoplastic resin having a ring and ball softeningpoint of 70 to 80 C. sold by Neville Chemical (30.; Nevillac 10coumaroneindene resin (Example 8); and Elvax ethylene-vinyl acetatecopolymer (Example 13). The compositions of these blends are given inTable III.

The resin kettle was heated by an electric mantel to 175 to C. withagitation until a homogeneous melt was formed. The sponge backing ofcommercial carpet tile was coated with the molten adhesive at 180 C. bydrawing down with a #12 wire wound bar. Each of these compositionsexhibited good pressure-sensitive adhesion.

TABLE III Weight percent composition of- Segmented copoly- Piecolastie"Nevillac" ester ElvaxQ elastomer Hard 10 1 Example 25 Twenty-sevenpounds of the segmented copolyester used in Example 4, 9 lbs. of LTP 115phenol-modified terpene resin (Example 9), 9 lbs. of Piccoumaron 410 HLpolyindene petroleum resin (Example 4), 55 lbs. of Neville R-27coumaz'one-indene resin (Example 8), and 0.5 lb. of Irganox 1010antioxidant (Example 1) were mixed in the same manner as in Example 1except that a 20 gallon kettle was used and the contents were heated bysteam to 180 C. The product had a melt viscosity of 14,000 centipoisesat 170 C. Particle boards were coated with the blend, 3 mils thick,using an Ashdee-Steinemann curtain coater. The coated boards were thenpassed underneath a heater to melt the adhesive layer and then nippedwith a 6-mil, plasticized poly(vinyl chloride) film. The laminate showedstrong, heat resistant adhesion.

Example 26' In the same manner as in Example 4, 0.5 lb. of the segmentedcopolyester of Example 4 was blended with 0.7 lb. of Piccolastic A 5styrene homopolymer (Example 4), 0.8 lb. of Piccoumaron 410 HI,polyindene petroleum resin (Example 4), and 0.01 lb. of Irganox" 1010antioxidant (Example 1). The blend had a melt viscosity of 11,000 cps.at 170 C. and was highly adhesive when applied molten. Kraft paper wascoated with this blend in a molten state. The coated kraft paper washeat sealed with uncoated kraft paper. The bond thus formed withstood apeeling stress of 200 g./ in. at 130 C. Corrugated paper board wasmanufactured with this adhesive using a hot melt corrugator.

Example 27 A dispersion was prepared by dissolving a 50:50 blend of thesegmented copolyester used in Example 4 and Cellolyn 21, a phthalateester of technical hydroabietyl alcohol obtained from rosin and having asoftening point of 60-70 C. available from Hercules Inc., in a trichloroethyleneisopropanol mixture, followed by dispersing the 19 solution inwater with Duponol WAQE, a sodium salt of technical lauryl alcoholsulfate surface active agent sold by E. I. du Pont de Nemours and Co.,Inc., and removing the organic solvents by the method described by Funckand Wolff in U.S. Pat. No. 3,296,172. The tensile properties of a filmprepared from the dispersion were essentially identical to those of afilm compression molded from a melt blend of the same resins.

Films were coated with the dispersion and dried, then heat-sealed at 140C. and 40 p.s.i.g. for 6 seconds. The 180 peel strength of Mylar toMylar adhesion was 275 g. per linear inch and the adhesion was found tobe very durable when the laminate was soaked in water. The 180 peelstrengths of heat-sealed laminates were 150 g. per linear inch forcellophane/cellophane bonds, and 90 g. per linear inch forpolypropylene/ polypropylene bonds.

Example 28 Example 27 was repeated except that each resin component wasdispersed separately in one-half the specified amount of solventmixture, water and surfactant, and the two dispersions were then mixedtogether. The 180 peel strengths were essentially the same as thoseobtained in Example 27.

Example 29 In the same manner as in Example 1, 20 parts of the segmentedcopolyester used in Example 4, 58.8 parts of Piccolastic A styrenehomopolymer (Example 4), 21.2 parts of Nevillac Hard phenol-modifiedcoumaroneindene resin (Examples 19-24), and 0.5 part of Irganox 1010antioxidant (Example 1) were blended into a homogeneous mixture. Theproduct had a melt viscosity of 10,000 cps. at 120 C. and a ring andball softening point of 127 C. The molten adhesive was spread thin overa particle board surface with a spatula and the printed side of aDecatone sheet was adhered to it and pressed uniformly. The laminate wasexposed for 14 days to 60 C. without any change in appearance.

Example 30 Ten grams of the segmented copolyester of Example 4 and g. ofCellolyn 21 rosin ester (Example 27) were dissolved in 200 ml. ofchloroform with agitation and warming. The clear yellow solution thusobtained was used to mend a torn scam in an inflatable polyvinylchloride plastic toy. The bond had good strength and durability.

Example 31 Neolite, a rubber composition shoe soling material A; inchthick with a specific gravity of 1.23 and a Shore A surface hardness of93-96- sold by Goodyear Tire and Rubber Co., and a polyvinylchloride/vinyl acetate shoe upper material were prepared for bonding bysanding the surfaces with 80 grit closed-coat aluminum oxide paper.Strips, 8 inch x 8 inch, of these substrates were coated with a moltenadhesive at 177 C. in a l0-mil. thick application using a #12 wire woundbar. The adhesive used in this example was prepared in the same manneras in Example 4 from 25 parts of the segmented copolyester of Example 4,50 parts of Piccolastic A 50 styrene homopolymer (Example 1), 25 partsof LTP 115 terpene resin (Example 9), and 0.5 part of Irganox 10 10antioxidant (Example 1). The adhesive on both the upper and solingsubstrates was activated with a heat lamp and the substrates werebrought together and held in position for seconds under a pressure of 70p.s.i.g. The bond had a 180 peel strength of 10 p.l.i. when tested at apeeling rate of 2 inches per minute.

Adhesive-coated Neolite and uncoated upper material were bondedlikewise. The bond showed a 180 peel strength of 8 p.l.i. In contrastwith conventional commercial practice, this high level of peel strengthwas obtained without the use of surface primers.

Example 32 In the manner described in Example 4, a pressure sensitiveadhesive was prepared by blending 25 parts of the segmented copolyesterof Example 4, 50 parts of Piccolastic A 5 styrene homopolymer (Example4), 25 parts of LTP terpene resin (Example 9), and 0.5 part of Irganox1010 antioxidant (Example 1). The sponge backing of a 4 inch x 4 inchsample of commercial carpet tile was coated with the molten adhesive at177 C. by drawing down with a #12 wire wound bar.

The coated surface gave strong adhesion on contact with Mylar film. The180 peel strength was 4.5 p.l.i. versus less than about 1 p.l.i. for acommercial carpet tile coated with a pressure sensitive adhesive. Theresistance to cieep rupture was measured by testing the time requiredfor bond failure under 1 p.s.i. shear stress. The adhesive of of thisinvention withstood for 200 minutes versus 80 minutes for a commercialmaterial. High temperature bond strength was determined by measuring thetemperature at which the adhesive bond failed when the bonded specimenwas heated at a moderate rate under 1 p.s.i. shear stress. The aboveadhesive withstood beyond C.

Example 33 In the manner described in Example 4 a pressure sensitiveadhesive composition was prepared by blending 25 parts of the segmentedcopolyester employed in Example 4, 40 parts of Piccodiene 2215, apolydicyclopentadiene resin having a ring and ball softening point of102 C., manufactured by "Pennsylvania Industrial Chemical Co., 35 partsof Piccolastic A 5 styrene homopolymer (-Example 4), and 0.5 part ofIrganox 1010 antioxidant (Example 1). In the manner of Example 32 thisadhesive was applied to the back of a foam-backed carpet tile in themolten state using a wire-wound rod. Subsequent testing showed that thiscomposition possessed a satisfactory level of tack and had a hightemperature bond failure temperature of 135 C.

Example 34 In a small cup heated to about 200 C. was placed 5 g. of thesegmented copolyester of Example 4, and 5 g. of Chlorowax 70, achlorinated parafiin wax containing 70 percent chlorine sold by DiamondAlkali Co. The molten resins were thoroughly mixed to give a transparentand tough thermoplastic material which was suitable for use as a hotmelt adhesive. Prolonged heating of this blend during preparation anduse was avoided because it tended to darken on long heating.

Example 35 A 1.0 pound sample of the mixture prepared in Example 4containing Piccoumaron 410 HL petroleum resin, Piccolastic A 5 styrenehomopolymer, Irganox 1010 antioxidant, and the segmented copolyester wasextrusion blended with an additional 3.45 pounds of the segmentedcopolyester described in Example 4. This blend was melt applied at 180C., to a woven polyester braid such as is used as the reinforcementlayer in the preparation of hydraulic hoses. Greater penetration of thebraid with attendant greater adhesion to the braid was noted as comparedwith a sample of the same segmented copolyester alone.

Example 36 A 9.5 g. portion of the segmented copolyester used in Example5 was dissolved in 200 ml. of boiling chloroform along with 0.5 g. ofPiccolastic A 50 styrene homopolymer (Example 1). After cooling, 220/3ply Dacron polyester thread was passed through the solution resulting ina 3 weight percent pick-up of the copolyester composition. The threeplies were observed to be bonded together and did not unravel. Thethread possessed good stiffness, but yet was still flexible. The coatingalso lowered the amount of fuzz on the surface of the thread.

21 Although the invention has been described and exemplified by way ofspecific embodiments, it is not intended that it be limited thereto. Aswill be apparent to those skilled in the art, numerous modifications andvariations of these embodiments can be made without departing from thespirit of the invention or the scope of the following claims.

What is claimed is: 1. A thermoplastic hot melt adhesive compositionwhich comprises, based on the total thermoplastic components,

(A) l to 99 percent by weight of thermoplastic segmented copolyesterelastomer consisting essentially of a multiplicity of recurring shortchain ester units and long chain ester units joined through esterlinkages, said short chain ester units amounting to 15 to 75 percent byweight of said copolyester and being of the formula O )R( i-ODO- andsaid long chain ester units amounting to 25 to 85 percent by weight ofsaid copolyester and being of the formula 0 O iR( i-0GO wherein R is thedivalent aromatic radical remaining after removal of the carboxyl groupsfrom aromatic dicarboxylic acid having a molecular weight of less than350, D is the divalent radical remaining after removal of the hydroxylgroups from organic diol having a molecular weight of less than 250, andG is the divalent radical remaining after removal of the terminalhydroxy groups from long chain glycol having an average molecular weightof 350 to 6000, said copolyester having a melt index of less than 150and a melting point of at least 125 C., and

(B) l to 99 percent by weight of low molecular weight thermoplasticresin which forms compatible mixtures with the segmented copolyester, isthermally stable at 150 C., and has a melt viscosity of less than 10,-000 centipoises at 200 C.

2. The composition of Claim 4 in which the short chain ester unitsamount to 15 to 65 percent by weight of the copolyester, the long chainester units amount to 35 to 85 percent by weight of the copolyester, andthe long chain glycol has a melting point of less than 55 C. and acarbon to oxygen ratio greater than 2.5.

3. The composition of Claim 2 in which an aryl phosphate plasticizer isalso present.

4. A thermoplastic hot melt adhesive composition which comprises, basedon the total thermoplastic components,

(A) 1 to 99 percent by weight of thermoplastic segmented copolyesterelastomer consisting essentially of a multiplicity of recurring shortchain ester units and long chain ester units joined through esterlinkages, said short chain ester units amounting to 15 to 75 percent byweight of said copolyester and being of the formula lull-013% and saidlong chain ester units amounting to 25 to 85 percent by weight of saidcopolyester and being of the formula II It wherein R is the divalentaromatic radical remaining after removal of the carboxyl groups fromaromatic dicarboxylic acid having a molecular weight of less than 350, Dis the divalent radical remaining after removal of the hydroxyl groupsfrom organic diol having a molecular weight of less than 250, and G 15the divalent radical remaining after removal of the 22 terminal hydroxylgroups from long chain glycol having an average molecular weight of 350to 6000, said copolyester having a melt index of less than 150 and amelting point of at least C., and

(B) 1 to 99 percent by weight of low molecular weight thermoplasticresin selected from the group consisting of hydrocarbon resins,bituminous asphalts, coal tar pitches, resins, phenolic resins,chlorinated aliphatic hydrocarbon waxes, chlorinated polynucleararomatic hydrocarbons, and mixtures thereof which form compatiblemixtures with the segmented copolyester, is thermally stable at 150 C.,and has a melt viscosity of less than 10,000 centipoises at 200 C.

5. The composition of claim 2 in which the thermoplastic compositioncomprises 5 to 95 percent by weight of segmented copolyester elastomerand 5 to 95 percent by weight of low molecular weight thermoplasticresin.

6. The composition of claim 2 which comprises 5 to 50 percent by weightof segmented copolyester elastomer and 50 to 95 percent by weight of lowmolecular weight thermoplastic resin.

7. The composition of Claim 2 which comprises 50 to 95 percent by weightof segmented copolyester elastomer and 5 to 50 percent by weight of lowmolecular weight thermoplastic resin.

8. The composition of Claim 5 in which the aromatic dicarboxylic acid isof 8 to 16 carbon atoms, the low molecular weight diol is aliphatic diolof 2 to 8 carbon atoms, and the long chain glycol is poly(alkyleneether) glycol in which the alkylene group is of 2 to 9 carbon atoms.

9. The composition of Claim 8 in which the short chain ester unitsamount to about 30 to 65 percent by weight of the copolyester, the longchain ester units amount to about 35 to 70 percent by Weight of thecopolyester, and the copolyester has a melt index of less than 50 and amelting point of at least C.

10. The composition of Claim 9 in which the aromatic dicarboxylic acidis selected from the group consisting of terephthalic acid, and mixturesof terephthalic and isophthalic acids, the low molecular weight diol isbutanediol, and the long chain glycol is polytetramethylene ether glycolhaving a molecular weight of 600 to 3000.

11. The composition of Claim 10 which comprises 15 to 45 percent byweight of segmented copolyester elastomer and 55 to 85 percent by weightof low molecular weight thermoplastic resin.

12. The composition of Claim 11 in which the low molecular weightthermoplastic resin is a mixture of at least two low molecular weightthermoplastic resins.

13. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a syrene polymer.

14. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a coumaroneindene resin.

15. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a bituminous asphalt.

16. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a rosin.

17. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a terpene resin.

18. The composition of Claim 12 in which one of the low molecular weightthermoplastic resins is a petroleum resin.

19. Method of preparing a thermoplastic hot melt adhesive compositionwhich comprises blending in molten form, based on the totalthermoplastic components,

(A) 1 to 99 percent by weight of thermoplastic segmented copolyesterelastomer consisting essentially of a multiplicity of recurring shortchain ester units and long chain ester units joined through esterlinkages,

23 said short chain ester units amounting to 15 to 75 percent by weightof said copolyester and being of the formula and said long chain esterunits amounting to 25 to 85 percent by weight of said copolyester andbeing of the formula O iR( io GO wherein R is the divalent aromaticradical remaining after removal of the carboxyl groups from aromaticdicarboxylic acid having a molecular weight of less than 350, D is thedivalent radical remaining after removal of the hydroxyl groups fromorganic diol having a molecular weight of less than 250, and G is thedivalent radical remaining after removal of the terminal hydroxyl groupsfrom long chain glycol having an average molecular weight of 350 to6000, said copolyester having a melt index of less than 150 and and amelting point of at least 125 C., and

(B) 1 to 99 percent by Weight of low molecular weight thermoplasticresin which forms compatible mixtures with the segmented copolyester, isthermally stable at 150 C., and has a melt viscosity of less than 10,000centipoises at 200 C.

20. The method of Claim 21 in which the short chain ester units amountto to 65 percent by weight of the copolyester, the long chain esterunits amount to 35 to 85 percent by weight of the copolyester, and thelong chain glycol has a melting point of less than 55 C. and a carbon tooxygen ratio greater than 2.5.

21. Method of preparing a thermoplastic hot melt adhesive compositionwhich comprises blending in molten form, based on the totalthermoplastic components,

(A) 1 to 99 percent by weight of thermoplastic segmented copolyesterelastomer consisting essentially of a multiplicity of recurring shortchain ester units and long chain ester units joined through esterlinkages, said short chain ester units amounting to 15 to 75 percent byweight of said copolyester and being of the formula and said long chainester units amounting to 25 to 85 percent by weight of said copolyesterand being of the formula i i G RC-O GO- wherein :R is the divalentaromatic radical remaining after removal of the carboxyl groups fromaromatic dicarboxylic acid having a molecular weight of less than 250, Dis the divalent radical remaining after removal of the hydroxyl groupsfrom organic diol having a molecular weight of less than 250, and G isthe divalent radical remaining after removal of the terminal hydroxylgroups from long chain glycol having an average molecular weight of 350to 6000, said copolyester having a melt index of less than 150 and amelting point of at least 125 C., and

(B) 1 to 99 percent by weight of low molecular weight thermoplasticresin selected from the group consisting of hydrocarbon resins,bituminous asphalts, coal tar pitches, rosins, phenolic resins,chlorinated aliphatic hydrocarbon waxes, chlorinated polynucleararomatic hydrocarbons, and mixtures thereof which forms compatiblemixtures with the segmented copolyester, is thermally stable at 150 C.,and has a melt viscosity of less than 10,000 centipoises at 200 C.

22. The method of Claim 19 in which the segmented copolyester is firstmelted and the low molecular weight thermoplastic resin is added to themelt.

23. The method of claim 19 in which the low molecular weightthermoplastic resin is first melted and the segmented copolyester isadded to the melt.

24. The method of Claim 19 in which the segmented copolyester and thelow molecular weight thermoplastic resin are blended together in finelydivided form and melted together.

25. Method of preparing an aqueous dispersion of a thermoplasticcomposition which comprises (A) dissolving the thermoplastic compositionof Claim 1 in a water-immiscible organic solvent,

(B) emulsifying the organic solvent solution in water,

and

(C) removing the organic solvent, thereby forming a dispersion.

26. The method of Claim 25 in which the short chain ester units amountto 15 to 65 percent by weight of the copolyester, the long chain esterunits amount to 35 to percent by weight of the copolyester, and the longchain glycol has a melting point of less than 55 C. and a carbon tooxygen ratio greater than 2.5.

27. The method of Claim 26 in which the low molecular weightthermoplastic resin is selected from the group consisting of hydrocarbonresins, bituminous asphalts, coal tar pitches, rosins, phenolic resins,chlorinated aliphatic hydrocarbon waxes, chlorinated polynucleararomatic hydrocarbons, and mixtures thereof.

28. Method of preparing an aqueous dispersion of a thermoplasticcomposition which comprises (A) dissolving thermoplastic segmentedcopolyester elastomer consisting essentially of a multiplicity ofrecurring short chain ester units and long chain ester units joinedthrough ester linkages, said short chain ester units amounting to 15 to75 percent by Weight of said copolyester and being of the formula andsaid long chain ester units amounting to 25 to 85 percent by weight ofsaid copolyester and being of the formula i ii --0 Ro-O Gowherein R isthe divalent aromatic radical remaining after removal of the carboxylgroups from aromatic dicarboxylic acid having a molecular weight of lessthan 350, D is the divalent radical remaining after removal of thehydroxyl groups from organic diol having a molecular weight of less than250, and G is the divalent radical remaining after removal of theterminal hydroxyl groups from long chain glycol having an averagemolecular weight of 350 to 6000, said copolyester having a melt index ofless than 150 and a melting point of at least C., in a water-immiscibleorganic solvent,

(B) dissolving low molecular weight thermoplastic resin which formscompatible mixtures with the segmented copolyester, is thermally stableat C., and has a melt viscosity of less than 10,000 centipoises at 200C., in a different water-immiscible organic solvent,

(C) emulsifying each organic solvent solution in water,

(D) removing the organic solvent from each emulsion,

thereby forming separate dispersions, and

(-E) mixing the dispersions together in such amounts that the finaldispersion contains, based on the total thermoplastic components, 1 to99 percent by weight of thermoplastic segmented copolyester elastomerand 1 to 99 percent by weight of low molecular weight thermoplasticresin.

25 29. The method of Claim 28 in which the short chain ester unitsamount to 15 to 65 percent by weight of the copolyester, the long chainester units amount to 35 to 85 percent by weight of the copolyester, andthe long chain glycol has a melting point of less than 55 C. and acarbon 5 to oxygen ratio greater than 2.5.

30. The method of Claim 29 in which the low molecular weightthermoplastic resin is selected from the group consisting of hydrocarbonresins, bituminous asphalts, coal 10 2 References Cited UNITED STATESPATENTS 3,023,192 12/ 1972 Shivers 26045.75 R 3,651,014 3/1972 Witsiepe26045.9 R 3,629,360 12/ 1971 Burkhart 260829 MAURICE J. WELSH, 111.,Primary Examiner W. F. PARKER, Assistant Examiner US. Cl. XJR.

111122; 156306, 332; 161140; 26019 N, 27 R, 28.5 AS, 33.6 UD, 33.8 UA,45.75 K, 45.9 R, 75 R, 829

jg gg UNITED STATES PATENT OFFICE I CERTIFICATE OF CORRECTION Patent Nog jl i DatedAuguSt 27, 1971+ Inventofls) George L,K, Hoh and AkiraIsukamoto It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

F601. 1, lines 11 and 12, delete "Claims priority, application '1Canada, Dec. 9, 1971, 129,800". 001. 3, line 58, "derirvatives" shouldread derivatives -col' 3., line 71, "bis(phydroxy" should readbis(p-hydroxy) Col. it, line 9, "Long" should read Copolyesterscontainin long col i line 31, "polyhexameth-" should read poly hexameth-Col 7, line 55, after "alone" the comma should be a period. Col. 9, line66, "1,3,5-trimethyl-2,L .-tris[3,5-ditertiarybutyl-h-hydroxyshould read1,3,5-trimethyl-2,l; ,6- tris[3,5-ditertiary-butyll -hydroxy C01. 18,line 7, "vPiccolastic" should read "Piccolastic" Col. 18,

line 18, "mantel" should read mantle Col. 20, line 7, "Irganox shoullread "Irganox" Col. 22, line 8, "resins" should read rosins col. 22,line 52, "syrene" should read styrene Col. 23, line 23, delete "and",first occurrence. v a

Signed and sealed this 7th day of January 1975 (SEAL) Attest:

MCCOY GIBSON JR, f c. MARSHALL DANN Attesting Officer Commissioner ofPatents 7

